WO2020243948A1 - Électrolyte polymère polymérisé in situ pour batteries au lithium-ion - Google Patents

Électrolyte polymère polymérisé in situ pour batteries au lithium-ion Download PDF

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Publication number
WO2020243948A1
WO2020243948A1 PCT/CN2019/090337 CN2019090337W WO2020243948A1 WO 2020243948 A1 WO2020243948 A1 WO 2020243948A1 CN 2019090337 W CN2019090337 W CN 2019090337W WO 2020243948 A1 WO2020243948 A1 WO 2020243948A1
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polymer electrolyte
precursor composition
monomers
electrolyte precursor
monomer
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PCT/CN2019/090337
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English (en)
Inventor
Shasha SU
Jinhua JIANG
Jing Feng
Hongping Li
Huichao LU
Zhixin XU
Jun Yang
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Evonik (Shanghai) Investment Management Co., Ltd.
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Priority to IL288632A priority Critical patent/IL288632B2/en
Priority to CA3140106A priority patent/CA3140106A1/fr
Priority to JP2021572001A priority patent/JP2022536290A/ja
Priority to PCT/CN2019/090337 priority patent/WO2020243948A1/fr
Priority to MX2021014981A priority patent/MX2021014981A/es
Priority to US17/616,932 priority patent/US20220344712A1/en
Priority to EP19932110.0A priority patent/EP3981042A4/fr
Priority to BR112021024444A priority patent/BR112021024444A2/pt
Priority to CN201980098870.8A priority patent/CN114207894A/zh
Priority to KR1020227000117A priority patent/KR20220017994A/ko
Publication of WO2020243948A1 publication Critical patent/WO2020243948A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L37/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an in-situ polymerized polymer electrolyte using e.g. cellulose separator for lithium metal batteries.
  • Lithium ion batteries are widely used in portable electronic devices, electric vehicles (EVs) , hybrid electric vehicles (HEVs) and energy storage systems.
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • Lithium metal-based batteries are an ideal anode candidate as it can offer the highest theoretical specific capacity (3860 mAh g -1 ) and the lowest redox potential (-3.04 V vs the standard hydrogen electrode) .
  • Polymer electrolyte which combines the advantages of liquid electrolyte and solid electrolyte greatly shows ideal ionic conductivity, excellent electrochemical performance at room temperature and no leakage of liquid. More importantly, polymer electrolyte can use rigid skeleton possessing good mechanical strength to suppress Li dendrite growth in recent research.
  • In-situ polymer electrolyte is thermally prepared by precursor solution which consists of organic solvent, lithium salt , polymerable monomer and thermal initiator.
  • precursor solution which consists of organic solvent, lithium salt , polymerable monomer and thermal initiator.
  • Vinylene carbonate (VC) can be polymerized into poly (vinylenecarbonate) (PVCA) which has superior mechanical property, wide-electrochemical stability window and excellent interfacial compatibility with electrode as a main ingredient in the solid electrolyte interface (SEI) .
  • SEI solid electrolyte interface
  • a cross-linking agent can facilitate the monomer polymerization at low content.
  • the combination of VC and cross-linking agent could form an excellent polymer skeleton.
  • cellulose membrane which possesses large number of micron pores, good mechanical strength and elasticity has broad application prospect in the in-situ polymerization. Thinner cellulose membrane has smaller lithium ion transmission resistance, which is more appropriate to achieve better battery performance.
  • PVCA poly (vinylene carbonate) based solid polymer electrolyte possess electrochemical stability window up to 4.5 V versus Li/Li + and ionic conductivity of 9.82 ⁇ 10 -5 S cm -1 at 50 °C for LiCoO 2 /Li batteries.
  • the LiCoO 2 /Li battery only delivered reversible capacity of about 97 mAh g -1 at a current density of 0.1 C, which was due to the low ionic conductivity of PVCA-SPE and large polarization at 25 °C.
  • J. Chai et al (J. Chai et al. ACS Apply Material Interfaces, Vol. 9 (2017) , pp 17897–17905) developed a PVCA-based polymer electrolytes via a facile in situ polymerization method, which possesses an ionic conductivity of 5.59 ⁇ 10 -4 S cm -1 and electrochemical stability window for 4.8 V vs Li + /Li at ambient temperature, and delivered capacity retention (88.7%) after 1000 cycles at 1.0 C for LiFe 0.2 Mn 0.8 PO 4 /graphite lithium ion batteries.
  • graphite was used as anode.
  • monomers e.g. unsaturated carbonated ester monomer and trimethylolpropane ethoxylate triacrylate may form an excellent polymer skeleton for polymer electrolyte, which shows excellent performance such as cycle performance and electrochemical stability window as compared with commercial liquid electrolytes when using lithium metal as anode.
  • Figure 1 shows the infrared test results proving that VC and trimethylolpropane ethoxylate triacrylate (ETPTA) had reacted completely according to Example 1.
  • ETPTA trimethylolpropane ethoxylate triacrylate
  • Figure 2 shows the scanning electron microscope (SEM) images of Li foil after cycled with the electrolytes prepared in Example 2 ( Figure 2 (a) ) and Comparative Example 1 ( Figure 2 (b) ) , respectively.
  • Figure 3 shows the cycle performance of the electrolytes prepared in Example 1, Example 2, Example 3 and Comparative Example 1 at 0.5C rate.
  • Figure 4 shows the electrochemical stability window test result of the polymer electrolyte prepared in Example 1, Example 2, Example 3, and Comparative Example 1.
  • Figure 5 shows the ionic conductivity of the polymer prepared in Example 1 (25%) , Example 2 (50%) and Example 3 (75%) .
  • Figure 5 (b) and Figure 5 (c) are enlarged views of the lower left corner of Figure 5 (a) .
  • the present invention provides monomers (i.e. a monomer composition or a composition of monomers) for preparing a polymer electrolyte precursor composition capable to form an in-situ polymerized polymer electrolyte, which comprise, consist essentially of, or consist of:
  • A1 a first monomer, which is an unsaturated carbonated ester monomer, preferably a monomer represented by formula (I) , more preferably vinylene carbonate (VC) ;
  • R represents H, F, methyl or ethyl
  • A2) a second monomer, represented by formula (II) , preferably trimethylolpropane ethoxylate triacrylate (ETPTA) ;
  • R represents methyl, -CH 2 OH, ethyl, or -CH 2 CH 2 OH, preferably R represents methyl, -CH 2 OH or ethyl; a, b, c each independently represents 0, 1, 2 or 3, and a+b+c ⁇ 2, preferably a+b+c ⁇ 3.
  • a polymer electrolyte precursor composition may be prepared, which in turn may be used to form an in-situ polymerized polymer electrolyte.
  • the mass ratio of the first monomer and the second monomer is 20: 0.5-20: 10, for example 20: 2-20: 5, most preferably 20: 3-20: 5.
  • the present invention further provides a polymer electrolyte precursor raw material composition for preparing a polymer electrolyte precursor composition capable to form an in-situ polymerized polymer electrolyte, which comprises, consists essentially of, or consists of:
  • the present invention further provides a polymer electrolyte precursor composition capable to form an in-situ polymerized polymer electrolyte, which comprises, consists essentially of, or consists of:
  • a lithium salt preferably lithium bis (trifluoromethanesulfonyl) imide
  • organic solvent preferably ethylene carbonate /dimethyl carbonate
  • the amount of the monomers is 5-80wt. %, for example, 10-80wt. %, 20-80wt. %, more preferably 25-75 wt. %based on the total weight of the polymer electrolyte precursor composition.
  • the mass ratio of the first monomer and the second monomer is 20: 0.5-20: 10, most preferably 20: 3-20: 5.
  • the polymer electrolyte precursor composition comprises an organic solvent.
  • the method for preparing the polymer electrolyte precursor composition capable to form an in-situ polymerized polymer electrolyte of the invention may be conventional, for example a method comprising the step of mixing the components of the polymer electrolyte precursor composition.
  • the present invention further provides a method to in-situ prepare a polymer electrolyte, comprising the steps as follows,
  • reaction of the first monomer and the second monomer may be schematically shown as follows,
  • the present invention further provides a polymer electrolyte, especially a gel polymer electrolyte, wherein the polymer electrolyte is formed by (polymerization of) a polymer electrolyte precursor composition comprising the first monomer and second monomer of the invention, particularly the monomers of the invention.
  • the present invention further provides a polymer electrolyte for rechargeable batteries, comprising a polymer which is the reaction product of the monomers of the invention with a free radical initiator.
  • the present invention further provides a polymer electrolyte for rechargeable batteries, comprising:
  • an organic solvent which contains an amount of an ionic salt effective to achieve an ionic conductivity of about 0.44 mS/cm or less.
  • the ionic salt is a lithium salt.
  • the amount of the monomers is 20-80wt. %, preferably 25-75 wt. %based on the total weight of the polymer electrolyte precursor composition.
  • the amount of lithium salt is around 25wt. %
  • the amount of the first monomer and the second monomer is above around 75 wt. %
  • the polymer electrolyte formed by the composition will be in all-solid state; if the amount of the first monomer and the second monomer is below around 25 wt. %, the polymerization of the monomer will not be satisfactory and cannot form a good gel state.
  • the amount of the first monomer and the second monomer is preferably ⁇ 75 wt. %and >25 wt. %based on the total weight of the polymer electrolyte composition or polymer electrolyte precursor composition.
  • the present invention further provides a polymer electrolyte prepared in-situ by the polymer electrolyte precursor composition according to the invention.
  • the polymer electrolyte may be prepared according to the conventional methods in the art.
  • the present invention further provides a rechargeable battery comprising an anode, a cathode, a microporous separator separating said anode and said cathode, and a gel polymer electrolyte of the present invention.
  • the present invention further provides a lithium ion battery comprising the polymer electrolyte prepared in-situ by (polymerization of) the polymer electrolyte precursor composition according to the invention.
  • the present invention further provides an electrochemical device comprising the polymer electrolyte according to the present invention.
  • the electrochemical device is a secondary battery.
  • the present invention further provides a device fabricated by a process comprising:
  • the polymerizing may be performed by heating.
  • the polymer electrolyte of the invention may be either in gel state (i.e., gel polymer electrolyte) or solid state (i.e., solid polymer electrolyte) , preferably, the polymer electrolyte is in gel state.
  • the gel or solid state of the polymer electrolyte may be adjusted by the amount of organic solvent in the polymer electrolyte precursor composition. For example, as shown in the Examples 1-3, when the polymer electrolyte precursor composition comprises no organic solvent, the obtained polymer electrolyte is in solid state; when the polymer electrolyte precursor composition comprises organic solvent for example 10%-70wt. %, the obtained polymer electrolyte is in gel state.
  • lithium ion batteries there is no special limitation to the types of lithium ion batteries that may use the electrolyte of the present invention.
  • the lithium ion batteries are LMBs.
  • the present invention further provides use of the monomers of the invention, or the polymer electrolyte precursor raw material composition of the invention, or the polymer electrolyte precursor composition of the invention, in preparation of an in-situ polymerized polymer electrolyte or an electrochemical device.
  • the separator may be surface modified or unmodified; the separator may have a thickness of less than 30 ⁇ m, even less than 20 ⁇ m; the porosity of the separator may be above 70%, even above 80%; the material of the separator may be e.g. cellulose or polytetrafluoroethylene (PTFE) .
  • PTFE polytetrafluoroethylene
  • the carbonated ester monomer is preferably vinylene carbonate (VC) , with chemical formula: C 3 H 2 O 3 , and CAS login No. 872-36-6.
  • VC vinylene carbonate
  • the second monomer is preferably trimethylolpropane ethoxylate triacrylate (ETPTA) , or other monomers with similar molecule structure with ETPTA such as trimethylolpropane triacrylate (TMPTA) , pentaerythritol triacrylate (PETA) and so on.
  • ETPTA trimethylolpropane ethoxylate triacrylate
  • TMPTA trimethylolpropane triacrylate
  • PETA pentaerythritol triacrylate
  • the trimethylolpropane ethoxylate triacrylate may have an average Mn of around 428 and a CAS login No. 28961-43-5.
  • the free radical initiator of the polymerization reaction of the monomers is for the thermal polymerization reaction of the monomers, and may be those conventional in the art.
  • free radical initiator or the polymerization initiator may include azo compounds such as 2, 2-azobis (2-cyanobutane) , 2, 2-azobis (methylbutyronitrile) , 2, 2′-azoisobutyronitrile (AIBN) , azobisdimethyl-valeronitrile (AMVN) and the like, peroxy compounds such as benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cumyl peroxide, hydrogen peroxide and the like, and hydroperoxides.
  • azo compounds such as 2, 2-azobis (2-cyanobutane) , 2, 2-azobis (methylbutyronitrile) , 2, 2′-azoisobutyronitrile (AIBN) , azobisdimethyl-valeronitrile (AMVN) and the like
  • peroxy compounds such as benzoyl peroxide, acetyl peroxide, dilauryl peroxid
  • AIBN 2, 2′-azobis (2, 4-dimethyl valeronitrile) (V65)
  • the free radical initiator may be selected from azobisisobutyronitrile (AIBN) , azobisisoheptanenitrile (ABVN) , benzoyl peroxide (BPO) , lauroyl peroxide (LPO) and so on. More preferably, the free radical initiator is azobisisobutyronitrile (AIBN) .
  • the amount of the free radical initiator is conventional.
  • the amount of the free radical initiator is 0.1-3 wt. %, more preferably around 0.5 wt. %based on the total weight of the monomers.
  • the polymerization initiator is decomposed at a certain temperature of 40 to 80 °C to form radicals, and may react with monomers via the free radical polymerization to form a gel polymer electrolyte.
  • the free radical polymerization is carried out by sequential reactions consisting of the initiation involving formation of transient molecules having high reactivity or active sites, the propagation involving re-formation of active sites at the ends of chains by addition of monomers to active chain ends, the chain transfer involving transfer of the active sites to other molecules, and the termination involving destruction of active chain centers.
  • the lithium salt is a material that is dissolved in the non-aqueous electrolyte to thereby resulting in dissociation of lithium ions.
  • the lithium salt may be those used conventional in the art, non-limiting examples may be at least one selected from lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) , lithium hexafluorophosphate (LiPF 6 ) , lithium difluorooxalate borate (LiODFB) , LiAsF 6 , LiClO 4 , LiN (CF 3 SO 2 ) 2 , LiBF 4 , LiSbF 6 , and LiCl, LiBr, LiI, LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
  • the lithium salt is preferably lithium bis (trifluoromethanesulfonyl) im
  • the amount of lithium salt is also conventional, for example 5-40wt. %, most preferably around 25wt. %based on the total weight of the polymer electrolyte precursor composition.
  • the organic solvent may be conventional in the art.
  • the organic solvent may be non-protic organic solvents such as N-methyl-2-pyrollidinone, propylene carbonate (PC) , ethylene carbonate (EC) , butylene carbonate (BC) , dimethyl carbonate (DMC) , diethyl carbonate (DEC) , ethylmethyl carbonate (EMC) , gamma-butyrolactone, 1, 2-dimethoxy ethane, tetrahydroxy furan, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, propylene carbon
  • the organic solvent is selected from ethylene carbonate /dimethyl carbonate (EC/DMC) , propylene carbonate (PC) , triethylene glycol dimethyl ether (TEGDME) and so on.
  • the amount of the organic solvent is conventional.
  • the amount of the organic solvent may be 0%-70wt. %, for example 0%-65wt. %, 0%-60wt. %, 0%-55wt. %, 5%-70wt. %, 5%-65wt. %, 5%-60wt. %, 5%-55wt. %, preferably 10%-70wt. %, 10%-65wt. %, 10%-60wt. %, 10%-55wt. %, more preferably 20%-50wt. %based on the total weight of the polymer electrolyte precursor composition.
  • pyridine triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinone, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride or the like may be added to the electrolyte.
  • the electrolyte may further include halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride.
  • the electrochemical device encompasses all kinds of devices that undergo electrochemical reactions.
  • Examples of the electrochemical device include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, capacitors and the like, preferably secondary batteries.
  • the secondary battery is fabricated by inclusion of the electrolyte in an electrode assembly composed of a cathode and an anode, which are faced opposite to each other with a separator therebetween.
  • the cathode is, for example, fabricated by applying a mixture of a cathode active material, a conductive material and a binder to a cathode current collector, followed by drying and pressing. If necessary, a filler may be further added to the above mixture.
  • the cathode current collector is generally fabricated to have a thickness of 3 to 500 ⁇ m.
  • materials for the cathode current collector there is no particular limit to materials for the cathode current collector, so long as they have high conductivity without causing chemical changes in the fabricated battery.
  • the materials for the cathode current collector may include stainless steel, aluminum, nickel, titanium, sintered carbon, and aluminum or stainless steel which was surface-treated with carbon, nickel, titanium or silver.
  • the current collector may be fabricated to have fine irregularities on the surface thereof so as to enhance adhesion to the cathode active material.
  • the current collector may take various forms including films, sheets, foils, nets, porous structures, foams and non-woven fabrics.
  • the conductive material is typically added in an amount of 1 to 50%by weight, based on the total weight of the mixture including the cathode active material.
  • conductive materials may include conductive materials including graphite such as natural or artificial graphite; carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; conductive fibers such as carbon fibers and metallic fibers; metallic powders such as carbon fluoride powder, aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives.
  • the binder is a component assisting in binding between the active material and conductive material, and in binding with the current collector.
  • the binder is typically added in an amount of 1 to 50%by weight, based on the total weight of the mixture including the cathode active material.
  • the binder may include polyvinylidene fluoride, polyvinyl alcohols, carboxymethylcellulose (CMC) , starch, hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrollidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM) , sulfonated EPDM, styrene butadiene rubber, fluoro rubber and various copolymers.
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM sulfonated EPDM
  • styrene butadiene rubber fluoro rubber and various copolymers
  • the filler is an optional ingredient used to inhibit cathode expansion.
  • the filler there is no particular limit to the filler, so long as it does not cause chemical changes in the fabricated battery and is a fibrous material.
  • the filler there may be used olefin polymers such as polyethylene and polypropylene; and fibrous materials such as glass fiber and carbon fiber.
  • the anode is fabricated by applying an anode active material to the anode current collector, followed by drying. If necessary, other components as described above may be further included.
  • the anode current collector is generally fabricated to have a thickness of 3 to 500 ⁇ m.
  • materials for the anode current collector there is no particular limit to materials for the anode current collector, so long as they have suitable conductivity without causing chemical changes in the fabricated battery.
  • materials for the anode current collector may include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel having a surface treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Similar to the cathode current collector, the anode current collector may also be processed to form fine irregularities on the surfaces thereof so as to enhance adhesive strength to the anode active material.
  • the anode current collector may be used in various forms including films, sheets, foils, nets, porous structures, foams and non-woven fabrics.
  • Examples of the anode active materials utilizable in the present invention include carbon such as non-graphitizing carbon and graphite-based carbon; metal composite oxides such as Li x Fe 2 O 3 (0 ⁇ x ⁇ 1) , Li x WO 2 (0 ⁇ x ⁇ 1) and Sn x Me 1-x Me′ y O z (Me: Mn, Fe, Pb or Ge; Me′: Al, B, P, Si, Group I, Group II and Group III elements of the Periodic Table of the Elements, or halogens; 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; and 1 ⁇ z ⁇ 8) ; lithium metals; lithium alloys; silicon-based alloys; tin-based alloys; metal oxides such as SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and Bi
  • the secondary battery according to the present invention may be, for example, a lithium metal secondary battery, a lithium-ion secondary battery, a lithium polymer secondary battery, lithium-ion polymer secondary battery or the like.
  • the secondary battery may be fabricated in various forms.
  • the electrode assembly may be constructed in a jelly-roll structure, a stacked structure, a stacked/folded structure or the like.
  • the battery may take a configuration in which the electrode assembly is installed inside a battery case of a cylindrical can, a prismatic can or a laminate sheet including a metal layer and a resin layer. Such a configuration of the battery is widely known in the art.
  • the invention provides a polymer electrolyte precursor composition capable to form a polymer electrolyte, comprising, consisting essentially of, or consisting of:
  • A) monomers consisting of vinylene carbonate (VC) and trimethylolpropane ethoxylate triacrylate (ETPTA) ;
  • the amount of the VC and ETPTA is 25-75 wt. %based on the total weight of the polymer electrolyte precursor composition; and the mass ratio of VC and ETPTA is around 20: 2-20: 5.
  • the amount of lithium bis (trifluoromethanesulfonyl) imide is preferably around 25wt. %based on the total weight of the polymer electrolyte precursor composition.
  • the amount of ethylene carbonate /dimethyl carbonate is preferably 0%-50wt. %based on the total weight of the polymer electrolyte precursor composition.
  • the present invention provides a novel polymer electrolyte by in-situ polymerization of the polymer electrolyte precursor composition of the invention.
  • the polymer electrolyte may be prepared in-situ and the thickness of the electrolyte may be conveniently controlled.
  • the combination of the monomers, e.g. the first monomer and the second monomer form an excellent polymer skeleton, which shows excellent cycle performance and higher electrochemical stability window as compared with that of commercial liquid electrolyte.
  • the polymer electrolyte is non-flameable, indicating that it is safer than traditional liquid electrolyte.
  • the electrolyte when lithium metal is used as anode, lithium dendrite formation can be inhibited owing to the electrolyte’s superior mechanical properties as shown in Figure 2.
  • the electrolyte also eliminates the consumption of a large amount of solvents in traditional lithium metal batteries, thus the electrolyte is especially suitable for use in LMBs.
  • the polymer electrolyte of the invention showed superior ionic conductivity, wider electrochemical window and better cycle performance.
  • the lithium metal batteries were prepared according to the following method:
  • Steps a) and b) were performed in a glove box filled with argon gas (H 2 O, O 2 ⁇ 0.5 ppm) .
  • a LiFePO 4 (LFP) cathode was prepared as follows. LFP, acetylene black, and poly (vinylidene difluoride) in the weight ratio of 80: 10: 10 were mixed to form a viscous slurry. Then, a flat carbon-coated aluminum foil was coated with the viscous slurry by the doctor blade process. The carbon-coated aluminum foil coated with the viscous slurry was dried at 70 °C for 1 hour in an air-circulating oven and further dried at 100 °Cunder high vacuum for 12 h to obtain a LiFePO 4 cathode. The mass loading of active material (LiFePO 4 ) was 5.3-6.2 mg cm -2 .
  • the precursor electrolyte solution was injected into a 2032 lithium battery with a cellulose separator which separated cathode and anode (Li foil) , then the cells were heated at 60 °C for 8 h and then 80 °C for 4 h.
  • polymer electrolyte of gel state without flowable liquid phase between the anode and cathode could be obtained.
  • the gel state of polymer electrolyte could be confirmed as the 2032 battery was disassembled.
  • FTIR Fourier transform infrared spectroscopy
  • polymer electrolyte of gel state without flowable liquid phase between the anode and cathode could be obtained.
  • the gel state of polymer electrolyte could be confirmed as the 2032 battery was disassembled.
  • polymer electrolyte of solid state could be obtained.
  • the solid state of polymer electrolyte could be confirmed as the 2032 battery was disassembled.
  • the cycle performance of cells was evaluated by using LiFePO 4 as the cathode and Li metal as the anode at room temperature on a LAND battery testing system (Wuhan Kingnuo Electronics Co., Ltd., China) .
  • the cut-off voltage was 4.2 V versus Li/Li + for charge (Li extraction) and 2.4 V versus Li/Li + for discharge (Li insertion) . All the related cells would be activated by a small current before cycling.
  • the test results are shown in Figure 3.
  • the solid points represents discharge capacity and the hollow points represents coulombic efficiency.
  • Figure 4 shows the electrochemical stability window of the polymer electrolytes and liquid electrolyte.
  • the liquid electrolyte of Comparative Example 1 showed an electrochemical stability window of approximately 4.6 V.
  • the polymer electrolytes had higher electrochemical stability windows than that of the liquid electrolyte.
  • the polymer electrolytes of Example 1, Example 2 and Example 3 according to the present invention showed a very stable electrochemical stability window of approximately 5V, which could contribute to better electrochemical performance.
  • a very stable electrochemical stability window of approximately 5V is very important, which makes it possible to use novel high-nickel content cathodes in batteries.
  • Alternating current (AC) impedance spectroscopy was measured in the CHI760e electrochemical workstation.
  • the electronic conductivity of gel-polymer electrolyte was measured by SS/GPE/SS cell with an applied voltage of 5 mV and the results were shown in Figure 5 and the ionic conductivity of the examples were calculated based on Figure 5 and summarized in Table 2 below.
  • PVCA poly (vinylene carbonate)
  • PVCA poly (vinylene carbonate)
  • the ionic conductivity of the solid polymer electrolyte of the invention (4.5 ⁇ 10 -5 S/cm in Example 3) is higher.
  • the ionic conductivity is much higher than that of traditional PEO-based polymer electrolyte which can only offer a very low ionic conductivity of about 2.1 ⁇ 10 -6 S/cm (K.
  • Example 1 wen et al. J. Mater. Chem. A, Vol. 6 (2018) , pp 11631–11663) . Furthermore, the ionic conductivities of the gel polymer electrolyte in Example 1 and Example 2 were comparable to the PVCA-based gel polymer electrolyte of prior art. (J. Chai et al. ACS Apply Material Interfaces, Vol. 9 (2017) , pp 17897–17905) .
  • LiFePO 4 cell using in-situ polymerized gel polymer electrolyte of Example 2 was disassembled in an argon glove box and then the cycled Li foil was immersed in dimethoxyethane (DME) for about 2 hours to remove LiTFSI.
  • DME dimethoxyethane
  • Li foil cycled for 40 times in commercial electrolyte was processed the same method as above. Then, the prepared Li foil samples were observed by SEM (Nova Nano SEM 230, FEI Company, U.S.A. ) .
  • the Li foil cycled in gel polymer electrolyte exhibited dense cobblestone structure with particle size of 10-15 ⁇ m which indicated uniform lithium deposition during cycles, and no lithium dendrites were detected. While after cycled in commercial liquid electrolyte for about only 40 times, Li dendrites could be observed obviously as shown in Figure 2 (b) and loose lithium deposition could be observed as shown in the small image on the upper right corner of Figure 2 (b) . Both Li dendrite and pulverized Li are harmful to batteries. The results indicated that the gel polymer electrolyte can effectively inhibit the formation of Li dendrite and suppress the pulverization of lithium foil.
  • lithium dendrite formation can be inhibited in LIBs with lithium metal anode, owing to the electrolyte’s superior mechanical properties.

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Abstract

Des monomères pour la préparation d'une composition de précurseur d'électrolyte polymère aptes à former un électrolyte polymère polymérisé in situ, qui comprennent, consistent essentiellement en, ou consistent en A1) un premier monomère et A2) un second monomère. L'invention concerne également une composition de matière première de précurseur d'électrolyte polymère, une composition de précurseur d'électrolyte polymère pouvant former un électrolyte polymère comprenant les monomères, un électrolyte polymère et un dispositif électrochimique.
PCT/CN2019/090337 2019-06-06 2019-06-06 Électrolyte polymère polymérisé in situ pour batteries au lithium-ion WO2020243948A1 (fr)

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IL288632A IL288632B2 (en) 2019-06-06 2019-06-06 In situ polymerized polymer electrolyte for lithium ion batteries
CA3140106A CA3140106A1 (fr) 2019-06-06 2019-06-06 Electrolyte polymere polymerise in situ pour batteries au lithium-ion
JP2021572001A JP2022536290A (ja) 2019-06-06 2019-06-06 リチウムイオン電池用のその場重合されたポリマー電解質
PCT/CN2019/090337 WO2020243948A1 (fr) 2019-06-06 2019-06-06 Électrolyte polymère polymérisé in situ pour batteries au lithium-ion
MX2021014981A MX2021014981A (es) 2019-06-06 2019-06-06 Electrolito de polimero polimerizado in situ para baterias de ion de litio.
US17/616,932 US20220344712A1 (en) 2019-06-06 2019-06-06 In-situ polymerized polymer electrolyte for lithium ion batteries
EP19932110.0A EP3981042A4 (fr) 2019-06-06 2019-06-06 Électrolyte polymère polymérisé in situ pour batteries au lithium-ion
BR112021024444A BR112021024444A2 (pt) 2019-06-06 2019-06-06 Eletrólito polimérico polimerizado in-situ para baterias de íon de lítio
CN201980098870.8A CN114207894A (zh) 2019-06-06 2019-06-06 用于锂离子电池的原位聚合的聚合物电解质
KR1020227000117A KR20220017994A (ko) 2019-06-06 2019-06-06 리튬 이온 전지용 인시츄 중합 고분자 전해질

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